Premordanted imbibition dye printing blank



April 1, 1969 w.J.wx-:YER1-s 3,435,761

` PREMORDANTED IMEIBITION DYE PRINTING BLANK Filed May 1o. 196e /2 DYE MOLECULE ,rr/6` 3 `waLTR J. WEYERrs INVENTOR BY ZK/7% MM A TTOR/VE Y United States Patent O 3,435,761 PREMORDANTED IMBIBITION DYE PRINTING BLANK Walter John Weyerts, Rochester, N.Y., assignor to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey Filed May 10, 1966, Ser. No. 549,060 Int. Cl. B41m 5 /12; B41n 3/00; G03c 7/02 U.S. Cl. 101-464 18 Claims ABSTRACT OF THE DISCLOSURE In dye imbibition printing blanks which include a support having coated thereon a hydrophilic colloid layer containing basic mordant which tends to diffuse through the colloid, there is incorporated in the outer stratum of the colloid layer a water soluble acid salt of an alkyl or aryl substituted polyalkoxy ether which prevents diffusion of the mordant out of the layer. Processes for preparing such dye imbibition printing blanks are provided. Relief imbibition printing processes are provided which feature applying to the surface of a colloid blank a water soluble acid salt of an alkyl or aryl substituted polyalkoxy ether.

This invention relates to photographic imbibition dye printing processes and materials. lIn one aspect, it relates to improved imbibition dye printing blanks.

The imbibition dye printing process is Well known. According to the common procedures, a tanned colloid relief image is `formed by exposure of a suitable sensitive layer on a support and differentially hardening the colloid layer, thereafter removing the colloid from the support in the regions not exposed by light. The resultant colloid relief image is then dyed and the dye image transferred to a blank by imbibition. In this manner subtractively colored Idye images may be obtained which faithfully reproduce a colored subject.

When using blanks containing diffusible basic mordants, there appears to be a tendency lfor the mordant or constituents thereof, to diffuse out of the blank into matrix in contact therewith as shown in FIG. l of the accompanying drawings. The result is that as repeated dye transfers are made from a given matrix more mordant diffuses into the matrix, combines with some of the dye and is held there. The matrix then takes up more dye than it should when it is re-dyed. When -a transfer is made from the re-dyed matrix more dye is imbibed onto the blank than originally and the color balance of a print is seriously altered. After a number of transfers, the matrix may become clogged resulting in a drop in the higher densities with repeated transfers. This problem is referred to herein as matrix poisoning. A further result is that since the diffusible constituents of the blank appear to diffuse back not only into the matrix but also are adsorbed by the `bared areas of the matrix support representing the highlights of the picture, the final print contains undesirable dye density in the highlight region.

Previously it has been suggested to apply acidic polymers over the surface of mordanted blanks to avoid the problems noted above. However, the specific acidic polymers proposed have caused either sticking or slipping between the -matrix and blank, or have resulted in undesirably low dye transfer definition or density after successive transfers. It therefore appears highly desirable to provide a class of materials which effectively prevent matrix poisoning, and which do not cause undesirable sticking or slipping between the matrix and blank, and which further provide good dye transfer definition and density after several successive transfers.

ICC

One object of this invention is to provide improved, novel blanks. Another object of this invention is to provide improved, novel imbibition blanks which are treated to prevent matrix poisoning. Still another object of this invention is to provide imbibiton blanks treated to substantially eliminate mordant diffusion. Another object of this invention is to provide novel imbibition blanks which do not stick or slip when pressed against a matrix film. A further object of this invention is to provide imbibition blanks which give good dye density and transfer definition, even after a number of transfers. Still another object of this invention is to provide -a process for preparing such improved imbibition blanks. Another object of this invention is to provide an improved relief imbibition printing process. Other objects of this invention will be apparent from the following disclosure and the appended claims.

In the accompanying drawings, in FIG. 1 is illustrated the manner in which diffusible mordant molecules or particles migrate from an imbibition blank to a matrix film with the adverse effects mentioned. In FIG. 2 is shown a similar view of the improved colloid blank of the invention. FIG. 3 is a view similar to FIG. 1 showing the manner in which the blank of FIG. 2 improves the quality of dye transfers and prevents clogging of the matrix and staining of the support.

In accordance with one embodiment of this invention, dye imbibition blanks are provided which include a support having a hydrophilic colloid layer thereon containing a basic mordant which tends to diffuse through the colloid, and an effective quantity of a Water soluble acid salt of an alkyl or aryl substituted polyalkoxy ether in the outer stratum of the hydrophilic colloid layer to inhibit or prevent diffusion of the mordant out of said layer. It has been found that the tendency of the mordant to diffuse to the surface, or out of the blank and into a colloid matrix, is effectively prevented with the novel blanks of the invention. At the same time, good dye transfer definition and density are obtained without problems of sticking or slipping.

In accordance with another embodiment of this invention, an improvement is provided in the process -for manufacturing mordanted dye imbibition blanks having a hydrophilic colloid layer coated on a support, which features applying to the surface of the hydrophilic colloid layer an acid salt of an alkyl or aryl substituted polyalkoxy ether.

In still another embodiment of the invention, an improvement is provided in a relief imbibition printing process that includes transfer of a soluble acid dyestulf from a colloid relief image to `a colloid blank containing a diffusible, basic mordant and fixing the dyestuff in the blank. This improvement features treating the surface of the blank with an acid salt of an alkyl or aryl substit-uted polyalkoxy ether prior to reacting the dyestuff with the mordant.

A wide variety of compounds which are the acid salts of alkyl or aryl su-bstituted polyalkoxy ethers can be employed, such as the alkali metal and ammonium sulfate, sulfonate and carboxylic acid salts of alkyl substituted polyalkoxy ethers. Good results are obtained with such salts which have from l to 100, and preferably l to 5 alkoxy groups, each alkoxy group containing from 2 to 4 car-bon atoms. An especially useful class of compounds are acid salts of polyalkoxyalkyl substituted aryl ethers. Preferred aryl groups are phenyl and naphthyl. The most useful class of acid salts employed in the invention has the following general formula:

wherein R represents hydrogen or a straight or branched chain alkyl substituent (including substituted alkyl and alkoxy) containing from 1 to 30, and preferably from 4 to 16 carbon atoms, such as butyl, butoxy, pentoxy, amyl, hexyl, heptyl, p-tertiary octyl, nonyl, decyl, decyloxy, dodecyl, pentadecyl and triacontanyl; n represents an integer of lfrom 1 lto 100, and preferably 1 to 5; B represents an aryl nucleus, such as phenyl or naphthyl; m represents a positive integer of from l to 2; and, X -represents an acid salt selected from the group consisting of the sulfate, sulfonate and carboxylic acid alkali metal, triethanolamine, and ammonium salts. When m is l, R is an alkyl substituent.

The following acid salts of substituted polyalkoxy ethers are useful in this invention: Stepanol B-129, nonylphenoxypolyethylene oxide sulfate, sodium salt; Stepanol B-153, ammonium alkylphenoxypolyoxyethylene sulfate; Steol 4N, ethoxylated fatty alcohol sulfate where the fatty alcohol base is lauryl alcohol and the cation is sodium; Steol 4T, same as 4N except cation is triethanolamine; Steol CS-460, same as 4N except fatty alcohol is stripped coconut; Steol CA-460, same as CS-460 except cation is ammonium salt; Triton 770, sodium salt of p-tert octylphenoxy (ethoxy)-3ethyl sulfate; Triton W-30, sodium salt of alkylarylpolyether sulfate; Triton X-202, sodium salt of alkylarylpolyether sulfate; Triton X-301, sodium salt of alkylarylpolyether sulfate; Triton X200, p-tertoctylphenoxy ethoxy ethyl sulfonate sodium salt; Sipon ES, sodium lauryl polyethoxy sulfate; Sipon EA, arnmonium lauryl polyethoxy sulfate; Sipex EST, sodium salt of tridecyl et-her sulfate; Sipex EA, ammonium salt of a lauryl polyethoxy sulfate; Cellopal 40, polyethoxyalkylphenol sulfonate, sodium salt; Cellopal 100, polyethoxyalkylphenol sulfonate, triethanolamine salt; Alipal CO-433, sodium salt of a sulfate ester of an alkylphenoxy-poly(ethyleneoxy) ethanol; Alipal CO-436, same as CO-433 except ammonium salt; Alipal EO-526, sodium salt of a sulfated alkylphenoxypoly(ethyleneoxy)ethanol; Alipal LO-436, ammonium salt of a sulfated straightchain-alkylphenoXy-poly(ethyleneoxy)ethanol; S-ulfotex BTS, straight-chain-alkylphenolethoxylate sulfo salt; Sulfotex DHS, sulfated alkylphenolethoxylate; Sulfotex LMT, fatty lalkylethoxylate sulfo salt; Sulfotex NTS, sulfated alkylphenolethoxylate. The preferred compounds are the soluble salts of p-tert.-octyl-phenoxyethyl sulfonate; nonyl phenoxypolyethoxide sulfate and lauryl-polyethoxy sulfate.

My invention will now be described with reference to the accompanying drawing.

FIG. 1 shows an enlarged cross-sectional view of the elements concerned, the manner in which ditfusible, perhaps low molecular weight mordant particles, wander out of the colloid layer 11 of gelatin carried on paper support into the dyed relief image 12 and iilm support 13, when dye is being transferred to the colloid blank to be mordanted onto mordant particles 15. As mentioned, this diffusion may clog the relief image, and adsorbed mordant on the support 13 or in a subbing layer thereon results in staining the highlight :region of the print.

When the blanks of the invention shown in FIG. 2 are substituted for the blanks of FIG. 1, the defects attributed to mordant diffusion are avoided. The blank is conveniently prepared by mordanting the colloid layer with a suitable basic mordant. For example, the mordant is added to a suitable quantity of colloid, such as gelatin with hardener and coated on a support to yield a blank as shown in FIG. 2 wherein a support 10 of paper or film is shown carrying gelatin layer 11 in which basic mordant particles 14 and 15 are dispersed. Thereafter, the blank is bathed for a short time in an aqueous solution of an acid salt of a polyalkoxyalkyl substituted arylether, adjusted to a pH of about 4.0 to 5.0 (e.g., with sodium hydroxide solution). If desired, the acid salt may be coated over the colloid surface from such a solution which may in addition contain a vehicle such as gelatin. This treatment of the blank appears to deposit the salt in high concentration as a coating or in an outer stratum of the blank substantially as shown in FIG. 2 according to which support 10 carries the colloid layer 11 containing diffusible and non-ditfusible particles 14 and 15 and a stratum of acid salt particles 16 and some particles 17 which may result from reaction between mordant and acid salt. When the blank of FIG. 2 is used for receiving transfers of dye images from dyed relief images, photographic quality is `improved in the manner shown in FIG. 3 of the drawings. T-he diffusible mordant particles 14 wandering toward the matrix film meet acid salt particles 16 and reacting therewith are prevented from wandering into the matrix film. The dye molecules 12 transfer undisturbed and are fixed on mordant particles 15 by reaction therewith.

The acid salts employed in this invention are applied to mordanted blanks from any convenient solution, such as an aqueous solution. Best results are obtained with aqueous solutions adjusted to a pH of 4.0 to 5.0, and using concentrations of about 0.5 to about 1.5 percent acid salt.

This invention is applicable to dye imbibition blanks containing any basic mordant. Typical useful basic mordants are described in Sprague et al., U.S. Patents 2,548,- 564, 2,484,430. Especially useful basic mordants are described in Minsk U.S. Patent 2,882,156 issued Apr. 14, 1959. The mordants described in the Minsk patent are derived from carbonyl-containing polymers and aminoguanidine, such as a vinyl polymer containing from about 30- 90% by weight of the recurring unit having the structure.

wherein n represents 0 or 1, R represents a hydrogen atom or an alkyl group of from 1 to 4 carbon atoms and X represents the acid radical of an inorganic acid such as hydrochloric acid or an organic acid such as lactic acid, glycolic acid, alkanesulfoni acids containing from 1 to 4 carbon atoms such as methanesulfonic acid, n-butanesulfonic acid, etc. or of a monobasic saturated aliphatic carboxylic acid containing from 2 to 4 carbon atoms such as acetic, propionic or butyric acids, the remaining to 10% of the resin molecule being unreacted vinyl oxocompound, for example, acrolein, ly-methyl acrolein or vinyl alkyl ketone or combinations of these with styrene or an alkyl methacrylate in the proportions of from about 10-15% by weight of the unreacted vinyl oxo-compound to from about -85% by weight of the styrene or alkyl methacrylate, where the starting copolymer contains these components in about a 1:1 molar ratio.

Mordanted blanks treated in accordance with this invention are useful for receiving acid dyes from hydrophilic colloid relief images according to prior art techniques. Any suitable acid dye stuif may be transferred to the treated blanks of the invention, such as Anthracene Yellow GR (400% pure Schultz No. 177), Fast Red S. Conc. (Colour Index 176), Pontacyl Green SN Ex. (Colour Index 737), Acid blue black (Colour Index 246), Acid Magenta 0 (Colour Index 692), Naphthol Green B Conc. (Colour Index 5), Brilliant Paper Yellow Ex. Conc. (Colour Index 364), Tartrazine (Colour Index 640), Metanil Yellow Conc. (Colour Index 138), Pontacyl Carmine 6B Ex. Conc. (Colour Index 57), Pontacyl Scarlet R Conc. (Colour Index 487) and Pontacyl Rubine R Ex. Conc. (Colour Index 179).

Gelatin and other hydrophilic colloids can be employed in the blanks of the invention, such as polyvinyl alcohol and any of the colloids (or dispersing agents) referred to in Beavers U.S. Patent 3,039,873 issued June 19, 1962, column 13.

This invention will be further illustrated by the following examples. Examples 1 and 2 demonstrate the superior results achieved when dye imbibition blanks containing diffusible basic mordants are treated with the acidic salts in accordance with the invention.

Example 1 A dye imbibition blank was prepared by soaking 454 g. of gelatin in 5360 cc. of distilled water until well swollen, and the mixture then heated to 40 C. to dissolve the gelatin. There Were then added some saponin solution as a coating aid, 65 cc. of 50% aqueous glycerine and 100 g. of a solution of the resinous mordant produced according to Example 1 of Minsk U.S. Patent 2,882,156 (issued Apr. 14, 1959), in dilute acetic acid. 'Ihe pH of the mixture was adjusted to approximately 4.2 and 27 cc. of 10% formaldehyde solution was added. The resulting solution was coated onto a cellulose acetate film support at the rate of approximately 1.25 g. of gelatin (dry weight) per square foot. The blank thus obtained was prewet for one minute in distilled water, and the excess Water was blown off by means of an air squeegee. The blank was then dipped for approximately 3 seconds in a solution of 1.0 percent (active agent) Stepanol B-129 (believed to be a 50 percent solution of nonylphenoxypolyethylene oxide sulfonate, sodium salt, manufactured by Stepan Chemical Co.) plus 0.5 percent citric acid, with the pH of the solution adjusted to 4.2 with sodium hydroxide. A series of six trensfers were made to these blanks using a gelatin relief matrix containing an acid yellow dye stuff (e.g., Anthracene Yellow GR, Schultz No. 177). The yellow dye stain in the minimum density areas of the matrix after the six transfers was only 0.03, measured through an appropriate blue filter. There was no loss of dye transfer density and the definition was better than transfers made with a control. In a control experiment, the same imbibition blank was employed but the process was altered by omitting treatment with the aqueous acid salt solution. The yellow dye stain in minimum density areas of the matrix of the control was 0.15 measured through the same blue filter.

Example 2 fers, the matrix showed a stain 0.18 in minimum density r areas.

Example 3 The procedure of Example 1 was followed except that after the blank was prewet with water, it was dipped for approximately 3 seconds in a 1 percent solution of sodium laurylpolyethoxy sulfate (Sipon ES, Alcolac Chemical Corp.) at a pH of 4.2. The matrix stain after Isix transfers was only 0.02.

The following examples show the unsatisfactory results obtained when imbbition blanks are treated with the polymeric acids proposed in the prior art.

Example 4 The procedure of Example 1 was followed except that after the blank was prewet with water, it was dipped for approximately 3 seconds in a 1 percent solution of sodium polyacrylate at a pH of 4.2. The matrix stain after six transfers was reduced to only 0.09 density. Higher concentrations of sodium polyacrylate were viscous and slippery and caused trouble in transfer operations, such as bad sticking between matrices and blanks.

Example 5 The procedure of Example 4 was followed except that the blank was dipped, after being prewet with water, in a 1 percent solution (pH 4.2) of low viscosity carboxymethyl cellulose. Matrix stain after six transfers of yellow dye was 0.04 density. However, the images obtained had a much lower transfer definition than those obtained in accordance with Example 1.

Example 6 The procedure of Example 5 was followed except that the blank was dipped, after being prewet with water, in a one percent solution of a sulfonated polystyrene (Lustrex 770). After six transfers, the matrix stain was 0.03, lbut there was an undesirablelowering of transfer density with each successive transfer.

The invention has been described in detail with particular reference to preferred embodiments thereof, but, it will be understood that variations and modifications can be effected within the spirit and scope of the invention described hereinabove and in the appended claims.

I claim:

1. A dye imbibition blank comp-rising a support having coated thereon a hydrophilic colloid layer containing a basic mordant which tends to diffuse through said colloid, at least the outer stratum of said colloid layer containing an effective quantity of an acid salt of an alkyl or aryl `substituted polyalkoxy ether to prevent diffusion of said Imordant out of said colloid layer.

2. The dye imbibition blank of claim 1 wherein said acid salt has the following general formula:

wherein R represents an alkyl substituent containing from 4 to 16 carbon atoms; B represents an aryl nucleus; m represents an integer of from 1 to 2; n represents an integer of from 1 to 5; Iand, X represents an acid salt selected from the group consisting of the sulfate, sulfonate, and carboxylic acid alkali metal, triethanolamine and ammonium salts.

3. The dye imbibition blank of claim 1 wherein said acid salt has the following general formula:

wherein R represents a substituent selected for the group consisting of hydrogen and an alkyl substituent containing from 1 to 30 carbon atoms; B represents an aryl nucleus; m represents an integer of from 1 to 2; n represents an integer of from 1 to 5; and, X represents an acid salt Selected from the group consisting of the sulfate, sulfonate, and carboxylic acid alkali metal, triethanolamine and ammonium salts, provided that when mi represents 1, R represents an alkyl substituent.

4. The process for manufacturing a dye imbibition blank which comprises coating a support with a hydrophilic colloid containing a basic mordant which tends to `diffuse through said colloid, and then applying to the surface of said colloid the acid salt of an alkyl or aryl substituted polyalkoxyalkyl ether.

5. The process of claim 4 wherein said acid salt has the following formula:

wherein R represents an alkyl substituent containing from 4 to 16 carbon atoms; n represents an integer of from 1 to 5; X represents an acid salt selected from the group consisting of the sulfate, sulfonate, and carboxylic acid alkali metal, triethanolamine and ammonium salts; B represents an aryl nucleus; and m represents an integer of from 1 to 2.

6. The process of claim 4 wherein said acid salt is the sodium salt of p-tertiary-octyl-phenoxyethoxy ethyl sulfonate.

7. The process of claim 4 wherein said acid salt is the sodium salt of nonylphenoxypolyethylene oxide sulfate.

8. The process of claim 4 wherein said acid salt is the sodium salt of laurylpolyethoxy sulfate.

9. In `a relief imbibition printing process wherein a soluble acid dyestufl is transferred from a colloid relief image to a colloid containing basic mordant which tends to diffuse through said colloid, the process of fixing said dyestuff in said colloid blank which comprises applying to the surface of said colloid bl-ank an acid salt of an alkyl or aryl substituted polyalkoxyalkyl ether, and then contacting said colloid relief image with said colloid blank to transfer the acid dyestuff to said colloid blank.

10. The relief imbibition printing process f claim 9 wherein said acid salt has the following general formula:

R-(B m 1--(O--CH2CH2 n-O-CHZ-CH2-X wherein R represents an alkyl substituent containing from 4 to 16 carbon atoms; B represents an aryl nucleus; m represents an integer of from 1 to 2; n represents an integer of from 1 to 5; and, X representsv an acid salt selected from the group consisting of the sulfate, sulfonate, and carboxylic acid alkali met-al, triethanolamine and ammonium salts.

11. The relief imbibition printing process of claim 9 wherein said acid salt is the sodium salt of p-tertiary-octylphenoxyethoxy ethyl sulfonate.

12. The relief imbibition printing process of claim 9 wherein said acid salt has the following general formula:

wherein R represents a substituent selected from the group consisting of hydrogen and an alkyl substituent containing from 1 to 30 carbon atoms; B represents an aryl nucleus; m represents an integer of from l to 2; n represents an integer of from 1 to 5; and, X represents an acid salt selected from the group consisting of the sulfate, sulfonate, and carboxylic acid alkali metal, triethanolamine and ammonium salts, provided that when m represents 1, R represents an alkyl substituent.

13. The process of claim 9 wherein said acid salt is the sodium salt of nonylphenoxypolyethylene oxide sulfate.

14. The process of claim 9 wherein said acid salt is the sodium salt of laurylpolyethoxy sulfate.

15. A dye imbibition blank comprising a support having coated thereon a hydrophilic colloid layer containing |a basic mordant which tends to diffuse through said colloid, at least the outer stratum of said colloid layer containing an effective quantity of an acid salt of an alkyl or aryl sustituted polyalkoxy ether to prevent diffusion of said mordant out of said colloid layer, said acid salt having the following general formula:

wherein R represents an alkyl substituent containing from 4 to 16 carbon atoms; B rep-resents an aryl nucleus; m represents an integer of from 1 to 2; n represents an integer of from 1 to 5; and, X represents an acid salt selected from the group consisting of the sulfate, sulfonate, and carboxylic acid alkali metal, triethanolamine and ammonium salts; and, said mordant is a vinyl polymer compound cnosisting of from -85% by weight of a recurring structural unit represented by the following general structure:

wherein R1 represents an alkyl group containing from 1-4 carbon atoms and X1 represents the radical of an 'acid selected from the group consisting of hydrochloric acid, lactic acid, glycolic acid, and alkanesulfonic acid containing from 1-4 canbon atoms and a monobasic saturated aliphatic carboxylic acid containing from 2-4 carbon atoms, and conversely from 50-15% by weight of a recurring vinyl alkyl ketone unit wherein the alkyl group contains from 1-4 carbon atoms and is the same alkyl radical as the said R1 radical.

16. The dye imbibition blank defined in claim 15 wherein said acid salt is the sodium salt of nonlyphenoxypolyethylene oxide sulfonate.

17. The dye imbibition blank defined in claim 15 wherein said acid salt is the sodium salt of p-tertiaryoctylphenoxy-ethoxy ethyl sulfonate.

18. The dye imbibition blank defined in claim 15 wherein said acid salt is the sodium salt of laurylpolyethoxy sulfate.

References Cited UNITED STATES PATENTS 2,548,575 4/1951 Weyerts 101-464 2,868,077 l/l959 Ryan et al.

3,271,147 9/1966 Bush 96-3 XR 3,312,549 4/ 1967 Salminen et al 96-3 XR DAVID KLEIN, Primary Examiner.

U.S. Cl. X.R. 96-3, 29, 57 

